EP1118596B1 - Alkali-free aluminoborosilicate glass and its use - Google Patents

Alkali-free aluminoborosilicate glass and its use Download PDF

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Publication number
EP1118596B1
EP1118596B1 EP00125339A EP00125339A EP1118596B1 EP 1118596 B1 EP1118596 B1 EP 1118596B1 EP 00125339 A EP00125339 A EP 00125339A EP 00125339 A EP00125339 A EP 00125339A EP 1118596 B1 EP1118596 B1 EP 1118596B1
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Prior art keywords
oxide
glass
glasses
weight
aluminoborosilicate glass
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EP00125339A
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German (de)
French (fr)
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EP1118596A2 (en
EP1118596A3 (en
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Ulrich Dr. Peuchert
Peter Dr. Brix
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Schott AG
Carl Zeiss AG
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Carl Zeiss AG
Schott Glaswerke AG
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the invention relates to an alkali-free aluminoborosilicate glass. object The invention also relates to uses of this glass.
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • AMLCDs Active Matrix Liquid Crystal Displays
  • TFTs Thin Film Transistors
  • PLCs Plasma Addressed Liquid Crystals
  • the glasses should have a high transparency over a wide spectral range (VIS, UV) and a low density to save weight.
  • VIS, UV spectral range
  • TFT displays (“chip on glass”) also requires the thermal adaptation to the thin film silicon material.
  • amorphous silicon This is usually deposited as amorphous silicon (a-Si) at low temperatures up to 300 ° C on the glass substrate.
  • a-Si amorphous silicon
  • the thermal expansion coefficient ⁇ 20/300 may vary between 2.9 ⁇ 10 -6 / K and 4.2 ⁇ 10 -6 / K. If crystalline Si layers are largely generated by high-temperature treatments above 700 ° C. or direct deposition by means of CVD processes, as desired also in thin-film photovoltaics, a substrate with a significantly reduced thermal expansion of up to 3.2 ⁇ 10 -6 / K or less is required ,
  • Suitable glasses should be industrially in sufficient quality (no bubbles, knots, inclusions), z. B. be economically produced on a float plant or in drawing process.
  • the production of thin ( ⁇ 1 mm) streak-free substrates of low surface waviness via drawing process requires a high devitrification stability of the glasses.
  • a disadvantage of the semiconductor microstructure shrinking ("compaction") of the substrate during manufacture, in particular in the case of TFT displays, can be counteracted by setting a suitable temperature-dependent viscosity characteristic of the glass.
  • the glasses of WO 98/27019 are with their very small shares of BaO and SrO susceptible to crystallization.
  • the glasses containing relatively little SiO 2 show, especially if they contain larger amounts of B 2 O 3 and / or MgO and are low in alkali, not sufficiently high chemical resistance. This concerns the glasses from WO 97/11919 and EP 672 629 A2.
  • the SiO 2 -rich variants of the last-mentioned document have only low Al 2 O 3 contents, which is disadvantageous for the crystallization behavior.
  • the glasses for hard disks described in JP 9-12333 A are comparatively Al 2 O 3 or B 2 O 3 arm, the latter component being only an optional one.
  • the glasses are highly alkaline earth metal containing and have a high thermal expansion, which makes them unsuitable for use in LCD or PV technology.
  • DE 196 17 344 C1 and DE 196 03 689 C1 of the applicant are alkali-free tin oxide-containing SiO 2 arms or low-Al 2 O 3 glasses with a coefficient of thermal expansion ⁇ 20/300 of about 3.7 ⁇ 10 -6 / K and very good chemical resistance. They are suitable for use in display technology. However, since they necessarily contain ZnO, they are not optimally suited for processing on a float plant. In particular, at higher contents ZnO (> 1.5% by weight) there is the danger of the formation of ZnO coatings on the glass surface by evaporation and subsequent condensation in the hot forming area.
  • JP 9-156 953 A also relates to alkali-free glasses for display technology which are Al 2 O 3 arms.
  • the temperature resistance of these glasses is not sufficient, as evidenced by the transformation temperatures of the sample glasses.
  • JP 10-25132A, JP 10-114538 A, J P 10-130034 A, J P 10-59741 A, J P 10-324526 A, J P 11-43350 A, JP 10-139467 A, JP 10-231139 A and JP 11-49520 A are very large and compositional ranges variable with many optional components for display glasses, each with one or more specific refining agents be added. However, these writings give no indication how targeted glasses with the complete described requirement profile can be obtained.
  • the glass contains between> 58 and 65 wt .-% SiO 2 . At lower levels, the chemical resistance deteriorates, at higher levels, the thermal expansion increases too low and increases the crystallization tendency of the glass. Preferred is a maximum level of 64.5 wt .-%.
  • the glass contains> 20 to 25 wt .-% Al 2 O 3 .
  • Al 2 O 3 has a positive effect on the temperature stability of the glass without raising the processing temperature too much. With a low content, the crystallization susceptibility of the glass increases.
  • a content of at least 20.5% by weight, in particular of at least 21% by weight, of Al 2 O 3 is preferred.
  • a content of at most 24% by weight of Al 2 O 3 is preferred.
  • the B 2 O 3 content is limited to at most 11.5 wt .-% in order to achieve a high transformation temperature T g . Also, higher levels would degrade the chemical resistance.
  • the B 2 O 3 content is at most 11 wt .-%.
  • the B 2 O 3 content is more than 6 wt .-%, in order to ensure good meltability and good crystallization resistance of the glass.
  • An essential glass component is the network-converting alkaline earth oxides. Especially by varying their proportions, a thermal expansion coefficient ⁇ 20 / 300 between 2.8 ⁇ 10 -6 / K and 3.6 ⁇ 10 -6 / K is achieved.
  • the individual oxides are present in the following proportions:
  • the glass contains 4 to ⁇ 6.5 wt.% MgO and> 4.5 to 8 wt.% CaO. Rather high proportions of the two components have a positive effect on the desired Low density and low processing temperature properties while rather low levels of crystallization resistance and promote chemical resistance.
  • the glass contains BaO, at least 0.5 wt .-%.
  • the BaO maximum level is limited to less than 5 wt .-%. That's how the good ones become Ensuring meltability and keeping the density low.
  • the glass can also be up to ⁇ 4 wt .-% of also comparatively heavy alkaline earth oxide containing SrO.
  • the limitation of this facultative Component to this low maximum level is especially for a low Density and good meltability of the glass advantageous.
  • SrO be present is, preferably at least 0.2 wt .-%.
  • the total content of BaO and SrO is at least> 3 wt .-%, to to ensure adequate crystallization stability.
  • the glass can contain up to 2% by weight of ZnO, preferably up to ⁇ 2% by weight of ZnO.
  • ZnO has a framework-loosening function as a network converter and has little influence on the thermal expansion of the alkaline earth oxides. It has a similar influence on the viscosity characteristic as B 2 O 3 .
  • the ZnO content is limited to at most 1.5 wt .-%. Higher levels would increase the risk of interfering ZnO deposits on a glass surface resulting from evaporation and subsequent condensation. can form in the hot forming area.
  • the glass is alkali-free.
  • Alkaline-free is here understood to mean essentially is free of alkali oxides, with impurities of less may contain as 1000 ppm.
  • the glasses can contain up to 2% by weight ZrO + TiO 2 , wherein both the TiO 2 content and the ZrO 2 content individually can be up to 2% by weight.
  • ZrO 2 advantageously increases the temperature stability of the glass. However, due to its poor solubility, it increases the risk of ZrO 2 -containing melt relics (so-called "zircon nests") in the glass. Therefore, it is preferable to dispense with the addition of ZrO 2 . Low levels of ZrO 2 , which result from the corrosion zirkon restroomn tub material, are not a problem.
  • TiO 2 advantageously lowers the solarization tendency, ie the decrease in the transmission in the visible wavelength range due to UV-VIS radiation. At levels greater than 2% by weight, color casts may occur by complexing with Fe 3+ ions present in the glass at low levels due to impurities in the raw materials used.
  • the glasses may contain conventional refining agents in conventional amounts: for example, it may contain up to 1.5% by weight of As 2 O 3 , Sb 2 O 3 , SnO 2 and / or CeO 2 . It is also possible to add 1.5% by weight of Cl - (for example as BaCl 2 ), F - (for example as CaF 2 ) or SO 4 2- (for example as BaSO 4 ). However, the sum of As 2 O 3 , Sb 2 O 3 , CeO 2, SnO 2, Cl - , F - and SO 4 2- should not exceed 1.5% by weight.
  • the glasses can be processed not only with the different drawing methods but also with the float method.
  • both ZrO 2 and SnO 2 can be dispensed with and still glasses with the mentioned property profile, in particular with high thermal and chemical resistance and with low crystallization tendency, are obtained.
  • the glasses have a high thermal shock resistance and good Devitrification stability on.
  • the glasses ideal for use as a substrate glass in display technology, especially for TFT displays, and in the Thin film photovoltaics.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)
  • External Artificial Organs (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention relates to an alkali-free aluminoborosilicate glass having a coefficient of thermal expansion alpha20/300 of between 2.8.10<-6>/K and 3.6.10<-6>/K, which has the following composition (in % by weight, based on oxide): silicon dioxide (SiO2)>58-65, boric oxide (B2O3)>6-11.5, aluminum oxide (Al2O3)>20-25, magnesium oxide (MgO) 4-<6.5, calcium oxide (CaO)>4.5-8, strontium oxide (SrO) 0-<4, barium oxide (BaO) 0.5-<5, with strontium oxide (SrO)+barium oxide (BaO)>3, zinc oxide (ZnO) 0-<2, and which is highly suitable for use as a substrate glass both in display technology and in thin-film photovoltaics.

Description

Gegenstand der Erfindung ist ein alkalifreies Aluminoborosilicatglas. Gegenstand der Erfindung sind auch Verwendungen dieses Glases.The invention relates to an alkali-free aluminoborosilicate glass. object The invention also relates to uses of this glass.

An Gläser für Anwendungen als Substrate in der Flüssigkristall-Flachdisplaytechnologie, z. B. in TN (Twisted Nematic)/STN (Super Twisted Nematic) - Displays, Active Matrix Liquid Crystal Displays (AMLCD's), Thin Film Transistors (TFT's) oder Plasma Adressed Liquid Crystals (PALC's) werden hohe Anforderungen gestellt. Neben einer hohen Temperaturwechselbeständigkeit sowie einer guten Resistenz bezüglich der im Herstellungsverfahren der Flachbildschirme eingesetzten aggressiven Chemikalien sollten die Gläser eine über einen weiten Spektralbereich (VIS, UV) hohe Transparenz sowie zur Gewichtseinsparung eine geringe Dichte aufweisen. Der Einsatz als Trägermaterial für integrierte Halbleiterschaltkreise z. B. in TFT-Displays ("chip on glass") erfordert darüber hinaus die thermische Anpassung an das Dünnfilmmaterial Silicium. Dieses wird üblicherweise als amorphes Silicium (a-Si) bei niedrigen Temperaturen bis 300 °C auf dem Glassubstrat abgeschieden. Durch eine nachfolgende Wärmebehandlung bei Temperaturen von ca. 600 °C rekristallisiert das amorphe Silicium partiell. Die resultierende teilweise kristalline poly-Si-Schicht ist aufgrund der a-Si-Anteile charakterisiert durch einen Wert der thermischen Ausdehnung von a 20/300 = 3,7 x 10-6/K. Je nach dem Verhältnis von a-Si zu poly-Si kann der thermische Ausdehnungskoeffizient α 20/300 zwischen 2,9 · 10-6/K und 4,2 · 10-6/K variieren. Werden durch Hochtemperaturbehandlungen oberhalb 700 °C bzw. direkte Abscheidung über CVD-Prozesse weitestgehend kristalline Si-Schichten generiert, so gewünscht auch in der Dünnschichtphotovoltaik, ist ein Substrat mit deutlich reduzierter thermischer Dehnung bis 3,2 x 10-6/K oder weniger erforderlich.To glasses for applications as substrates in liquid crystal flat panel display technology, e.g. For example, TN (Twisted Nematic) / STN (Super Twisted Nematic) displays, Active Matrix Liquid Crystal Displays (AMLCDs), Thin Film Transistors (TFTs), or Plasma Addressed Liquid Crystals (PALCs) have high requirements. In addition to a high thermal shock resistance and a good resistance to the aggressive chemicals used in the production process of flat screens, the glasses should have a high transparency over a wide spectral range (VIS, UV) and a low density to save weight. The use as a carrier material for semiconductor integrated circuits z. As in TFT displays ("chip on glass") also requires the thermal adaptation to the thin film silicon material. This is usually deposited as amorphous silicon (a-Si) at low temperatures up to 300 ° C on the glass substrate. By a subsequent heat treatment at temperatures of about 600 ° C, the amorphous silicon recrystallized partially. The resulting partially crystalline poly-Si layer is characterized by a thermal expansion value of a 20/300 = 3.7 × 10 -6 / K due to the a-Si content. Depending on the ratio of a-Si to poly-Si, the thermal expansion coefficient α 20/300 may vary between 2.9 × 10 -6 / K and 4.2 × 10 -6 / K. If crystalline Si layers are largely generated by high-temperature treatments above 700 ° C. or direct deposition by means of CVD processes, as desired also in thin-film photovoltaics, a substrate with a significantly reduced thermal expansion of up to 3.2 × 10 -6 / K or less is required ,

Für Anwendungen in der Display- und Photovoltaiktechnologie ist femer die Abwesenheit von Alkaliionen Bedingung. Herstellungsbedingte Anteile von Natriumoxid unterhalb 1000 ppm sind in Hinblick auf die i. a. "vergiftende" Wirkung durch Eindiffusion von Na+ in die Halbleiterschicht noch tolerierbar.For applications in the display and photovoltaic technology, the absence of alkali ions is also a condition. Manufacturing-related proportions of sodium oxide below 1000 ppm are still tolerable in view of the ia "poisoning" effect by diffusion of Na + into the semiconductor layer.

Geeignete Gläser sollten großtechnisch in ausreichender Qualität (keine Blasen, Knoten, Einschlüsse), z. B. auf einer Floatanlage oder in Ziehverfahren wirtschaftlich produzierbar sein. Besonders die Herstellung dünner (< 1 mm) streifenfreier Substrate von geringer Oberflächenwelligkeit über Ziehverfahren erfordert eine hohe Entglasungsstabilität der Gläser. Einem auf die Halbleiter-Microstruktur nachteilig wirkenden Schrumpf ("compaction") des Substrates während der Herstellung, insbesondere im Falle von TFT-Displays, kann durch Einstellen einer geeigneten temperaturabhängigen Viskositätskennlinie des Glases entgegengewirkt werden. Hinsichtlich der thermischen Prozeßund Formstabilität sollte es bei einerseits nicht zu hohen Schmelz- und Verarbeitungs (VA) -temperaturen, d. h. bei einem VA≤ 1350 °C, eine ausreichend hohe Transformationstemperatur, d. h. Tg > 700°C aufweisen.Suitable glasses should be industrially in sufficient quality (no bubbles, knots, inclusions), z. B. be economically produced on a float plant or in drawing process. In particular, the production of thin (<1 mm) streak-free substrates of low surface waviness via drawing process requires a high devitrification stability of the glasses. A disadvantage of the semiconductor microstructure shrinking ("compaction") of the substrate during manufacture, in particular in the case of TFT displays, can be counteracted by setting a suitable temperature-dependent viscosity characteristic of the glass. With regard to the thermal process and dimensional stability, it should have a sufficiently high transformation temperature, ie T g > 700 ° C., on the one hand, if the melting and processing (V A ) temperatures are not too high, ie at a V A ≦ 1350 ° C.

Die Anforderungen an Glassubstrate für die LCD-Displaytechnologie bzw. Dünnschicht-Photovoltaik-Technologie sind auch in "Glass Substrates for AMLCD applications: properties and implications" von J.C. Lapp, SPIE Proceedings, Vol. 3014, Invited paper (1997) beschrieben bzw. in "Photovoltaik-Strom aus der Sonne" von J. Schmid, Verlag C.F. Müller, Heidelberg 1994.The requirements for glass substrates for LCD display technology or Thin-film photovoltaic technology is also available in "Glass Substrates for AMLCD applications: properties and implications "by J.C. Lapp, SPIE Proceedings, Vol. 3014, Invited paper (1997) or in "Photovoltaic Electricity from the Sun "by J. Schmid, Verlag C.F. Müller, Heidelberg 1994.

Das genannte Anforderungsprofil wird am ehesten durch Erdalkalialuminoborosilicatgläser erfüllt. Die bekannten und in den folgenden Schriften beschriebenen Gläser für Display- oder Solarzellensubstrate weisen jedoch noch Nachteile auf und erfüllen nicht den gesamten Anforderungskatalog:The mentioned requirement profile is most likely due to alkaline earth aluminoborosilicate glasses Fulfills. The known and described in the following documents However, glasses for display or solar cell substrates still have Disadvantages and do not meet the entire catalog of requirements:

Zahlreiche Schriften beschreiben Gläser, mit geringen MgO- und/oder CaO-Gehalten:JP 9-169 538 A, JP 4-160 030 A, JP 9-100 135 A, EP 714 862 A1, EP 341 313 B1, US 5,374,595, JP 9-48632 A, JP 8-295530 A, WO 97/11919 und WO 97 11920. Diese Gläser besitzen nicht die gewünschte Schmelzbarkeit, was sehr hohe Temperaturen bei den Viskositäten 102 dPas und 104 dPas bestätigen, und weisen relativ hohe Dichten auf. Gleiches gilt für die MgO-freien Gläser der DE 37 30 410 A1, US 5,116,787 und US 5,116,789.Numerous documents describe glasses with low MgO and / or CaO contents: JP 9-169 538 A, JP 4-160 030 A, JP 9-100 135 A, EP 714 862 A1, EP 341 313 B1, US Pat. No. 5,374,595, US Pat. JP 9-48632 A, JP 8-295530 A, WO 97/11919 and WO 97 11920. These glasses do not possess the desired meltability, which confirm very high temperatures at the viscosities 10 2 dPas and 10 4 dPas, and have relatively high densities on. The same applies to the MgO-free glasses of DE 37 30 410 A1, US 5,116,787 and US 5,116,789.

Andererseits zeigen Gläser mit hohen Gehalten an MgO, wie sie in JP 61-123 536 A beschrieben sind, Mängel hinsichtlich ihrer chemischen Beständigkeit sowie ihres Entglasungs- und Entmischungverhaltens.On the other hand, glasses with high levels of MgO, as described in JP 61-123 536 A, defects in their chemical resistance as well as their devitrification and demixing behavior.

Auch die Gläser der WO 98/27019 sind mit ihren sehr geringen Anteilen an BaO und SrO kristallisationsanfällig.The glasses of WO 98/27019 are with their very small shares of BaO and SrO susceptible to crystallization.

Gläser mit hohen Gehalten an den schweren Erdalkalioxiden BaO und/oder SrO, wie sie in EP 341313 B1 beschrieben sind, besitzen unerwünscht hohe Dichten und sind nicht gut schmelzbar. Dies gilt auch für die Gläser der JP 10-72237 A. Nachweislich der Beispiele weisen die Gläser hohe Temperaturen bei den Viskositäten 104 dPas und 102 dPas auf.Glasses with high contents of the heavy alkaline earth oxides BaO and / or SrO, as described in EP 341313 B1, have undesirably high densities and are not readily fusible. This also applies to the glasses of JP 10-72237 A. As can be seen from the examples, the glasses have high temperatures at the viscosities 10 4 dPas and 10 2 dPas.

Auch Gläser mit geringen Borsäuregehalten weisen zu hohe Schmelztemperaturen bzw. aufgrund dessen bei verfahrensbedingt vorgegebenen Schmelzund Verarbeitungstemperaturen zu hohe Viskositäten auf. Dies betrifft die Gläser aus JP 10-45422 A, JP 9-263421 A und JP 61-132536 A. In Kombination mit niedrigen BaO-Gehalten weisen solche Gläser außerdem eine hohe Entglasungsneigung auf.Even glasses with low boric acid contents have too high melting temperatures or due to the fact that, given process-related melting and Processing temperatures to high viscosities. This concerns the Glasses of JP 10-45422 A, JP 9-263421 A and JP 61-132536 A. In combination with low BaO levels, such glasses also exhibit a high devitrification tendency.

Dagegen zeigen Gläser mit hohen Anteilen an Borsäure, wie sie beispielsweise in US 4,824,808 beschrieben sind, keine ausreichende Temperaturbeständigkeit und chemische Beständigkeit, insbesondere gegenüber salzsauren Lösungen.In contrast, glasses with high levels of boric acid, as for example in US 4,824,808, not sufficient temperature resistance and chemical resistance, especially to hydrochloric acid Solutions.

Auch die Gläser, die relativ wenig SiO2 enthalten, zeigen, insbesondere wenn sie größere Mengen an B2O3 und/oder MgO enthalten und erdalkaliarm sind, keine ausreichend hohe chemische Beständigkeit. Dies betrifft die Gläser aus WO 97/11919 und EP 672 629 A2. Die SiO2-reicheren Varianten der letztgenannten Schrift weisen nur geringe Al2O3-Anteile auf, was nachteilig für das Kristallisationsverhalten ist.Also, the glasses containing relatively little SiO 2 show, especially if they contain larger amounts of B 2 O 3 and / or MgO and are low in alkali, not sufficiently high chemical resistance. This concerns the glasses from WO 97/11919 and EP 672 629 A2. The SiO 2 -rich variants of the last-mentioned document have only low Al 2 O 3 contents, which is disadvantageous for the crystallization behavior.

Die in JP 9-12333 A beschriebenen Gläser für Festplatten sind vergleichsweise Al2O3- bzw. B2O3-arm, wobei letztgenannte Komponente nur eine fakultative ist. Die Gläser sind hoch erdalkalioxidhaltig und besitzen eine hohe thermische Dehnung, die sie für den Einsatz in der LCD- bzw. PV-Technologie ungeeignet macht.The glasses for hard disks described in JP 9-12333 A are comparatively Al 2 O 3 or B 2 O 3 arm, the latter component being only an optional one. The glasses are highly alkaline earth metal containing and have a high thermal expansion, which makes them unsuitable for use in LCD or PV technology.

DE 42 13 579 A1 beschreibt Gläser für TFT-Anwendungen mit thermischen Ausdehnungskoeffizienten < 5,5 x 10-6/K, ausweislich der Beispiele ≥4,0 x 10-6/K. Diese Gläser mit relativ hohen Anteilen an B2O3 bei vergleichsweise niedrigen SiO2-Gehalten sind nicht sehr chemisch resistent, insbesondere nicht gegenüber verdünnter Salzsäure.DE 42 13 579 A1 describes glasses for TFT applications with thermal expansion coefficients <5.5 x 10 -6 / K, as shown by the examples ≥ 4.0 x 10 -6 / K. These glasses with relatively high proportions of B 2 O 3 at comparatively low SiO 2 contents are not very chemically resistant, in particular not to dilute hydrochloric acid.

DE 196 01 022 A1 beschreibt Gläser aus einem sehr variablen Zusammensetzungesbereich, die zwingend ZrO2 und SnO enthalten. Diese Al2O3-armen Gläser neigen aufgrund ihres ZrO2-Anteils zu Glasfehlern. DE 196 01 022 A1 describes glasses from a very variable composition range, which necessarily contain ZrO 2 and SnO. These Al 2 O 3 poor glasses tend to glass defects due to their ZrO 2 content.

Aus DE 196 17 344 C1 und DE 196 03 689 C1 der Anmelderin sind alkalifreie zinnoxidhaltige SiO2-arme bzw. Al2O3-arme Gläser mit einem thermischen Ausdehnungskoeffizieten α20/300 von ca. 3,7 · 10-6/K und sehr guten chemischen Beständigkeiten bekannt. Sie sind geeignet für den Einsatz in der Displaytechnik. Da sie jedoch zwingend ZnO enthalten, sind sie insbesondere für eine Verarbeitung auf einer Floatanlage nicht optimal geeignet. Insbesondere bei höheren Gehalten ZnO (> 1,5 Gew. -%) besteht nämlich die Gefahr der bildung von ZnO-Belägen auf der Glasoberfläche durch Verdampfung und anschließende Kondensation im Heißformgebungsbereich.DE 196 17 344 C1 and DE 196 03 689 C1 of the applicant are alkali-free tin oxide-containing SiO 2 arms or low-Al 2 O 3 glasses with a coefficient of thermal expansion α 20/300 of about 3.7 · 10 -6 / K and very good chemical resistance. They are suitable for use in display technology. However, since they necessarily contain ZnO, they are not optimally suited for processing on a float plant. In particular, at higher contents ZnO (> 1.5% by weight) there is the danger of the formation of ZnO coatings on the glass surface by evaporation and subsequent condensation in the hot forming area.

Auch JP 9-156 953 A betrifft alkalifreie Gläser für die Displaytechnik, die Al2O3-arm sind. Die Temperaturbeständigkeit dieser Gläser ist, wie die Transformationstemperaturen der Beispielgläser belegen, nicht ausreichend.JP 9-156 953 A also relates to alkali-free glasses for display technology which are Al 2 O 3 arms. The temperature resistance of these glasses is not sufficient, as evidenced by the transformation temperatures of the sample glasses.

In den ungeprüften japanischen Veröffentlichungen JP 10-25132 A, JP 10-114538 A, J P 10-130034 A, J P 10-59741 A, J P 10-324526 A, J P 11-43350 A, JP 10-139467 A, JP 10-231139 A und JP 11-49520 A werden sehr große und mit vielen fakultativen Komponenten variierbare Zusammensetzungsbereiche für Displaygläser genannt, denen jeweils ein oder mehrere bestimmte Läuterungsmittel zugesetzt werden. Diese Schriften geben jedoch keinerlei Hinweise, wie gezielt Gläser mit den kompletten beschriebenen Anforderungsprofil erhalten werden können.In Japanese Unexamined Publication JP 10-25132A, JP 10-114538 A, J P 10-130034 A, J P 10-59741 A, J P 10-324526 A, J P 11-43350 A, JP 10-139467 A, JP 10-231139 A and JP 11-49520 A are very large and compositional ranges variable with many optional components for display glasses, each with one or more specific refining agents be added. However, these writings give no indication how targeted glasses with the complete described requirement profile can be obtained.

Es ist Aufgabe der Erfindung, Gläser bereitzustellen, die die genannten physikalischen und chemischen Anforderungen an Glassubstrate für Flüssigkristall-Displays, insbesondere für TFT-Displays, und für Dünnschichtsolarzellen, insbesondere auf Basis von µc-Si gestellt wird, erfüllen, Gläser, die eine hohe Temperaturbeständigkeit, einen prozeßgünstigen Verarbeitungsbereich und eine ausreichende Entglasungsstabilität aufweisen.It is an object of the invention to provide glasses containing the said physical and chemical requirements for glass substrates for liquid crystal displays, especially for TFT displays, and for thin-film solar cells, is made in particular on the basis of μc-Si, glasses that have a high Temperature resistance, a process-friendly processing area and have sufficient devitrification stability.

Die Aufgabe wird durch Aluminoborosilicatgläser gemäß dem Hauptanspruch gelöst.The object is achieved by Aluminoborosilicatgläser according to the main claim solved.

Das Glas enthält zwischen > 58 und 65 Gew.-% SiO2. Bei geringeren Gehalten verschlechtert sich die chemische Beständigkeit, bei höheren Anteilen nimmt die thermische Ausdehnung zu geringe Werte an und nimmt die Kristallisationsneigung des Glases zu. Bevorzugt ist ein Höchstgehalt von 64,5 Gew.-%. The glass contains between> 58 and 65 wt .-% SiO 2 . At lower levels, the chemical resistance deteriorates, at higher levels, the thermal expansion increases too low and increases the crystallization tendency of the glass. Preferred is a maximum level of 64.5 wt .-%.

Das Glas enthält > 20 bis 25 Gew.-% Al2O3. Al2O3 wirkt sich positiv auf die Temperaturstabilität des Glases, ohne die Verarbeitungstemperatur zu sehr anzuheben. Bei einem geringen Gehalt erhöht sich die Kristallisationsfälligkeit des Glases. Bevorzugt ist ein Gehalt von wenigstens 20,5 Gew.-%, insbesondere von wenigstens 21 Gew.-% Al2O3. Bevorzugt ist ein Gehalt von höchstens 24 Gew.-% Al2O3.The glass contains> 20 to 25 wt .-% Al 2 O 3 . Al 2 O 3 has a positive effect on the temperature stability of the glass without raising the processing temperature too much. With a low content, the crystallization susceptibility of the glass increases. A content of at least 20.5% by weight, in particular of at least 21% by weight, of Al 2 O 3 is preferred. A content of at most 24% by weight of Al 2 O 3 is preferred.

Der B2O3-Gehalt ist auf höchstens 11,5 Gew.-% beschränkt, um eine hohe Transformationstemperatur Tg zu erzielen. Auch würden höhere Gehalte die chemische Beständigkeit verschlechtern. Vorzugsweise beträgt der B2O3-Gehalt höchstens 11 Gew.-%. Der B2O3-Gehalt beträgt mehr als 6 Gew.-%, um eine gute Schmelzbarkeit und die gute Kristallisationsbeständigkeit des Glases zu gewährleisten.The B 2 O 3 content is limited to at most 11.5 wt .-% in order to achieve a high transformation temperature T g . Also, higher levels would degrade the chemical resistance. Preferably, the B 2 O 3 content is at most 11 wt .-%. The B 2 O 3 content is more than 6 wt .-%, in order to ensure good meltability and good crystallization resistance of the glass.

Ein wesentlicher Glasbestandteil sind die netzwerkwandelnden Erdalkalioxide. Vor allem durch Variation ihrer Anteile wird ein thermischer Ausdehnungskoeffizient α20/300 zwischen 2,8 · 10-6/K und 3,6 · 10-6/K erzielt. Die einzelnen Oxide liegen in den folgenden Anteilen vor:An essential glass component is the network-converting alkaline earth oxides. Especially by varying their proportions, a thermal expansion coefficient α20 / 300 between 2.8 · 10 -6 / K and 3.6 · 10 -6 / K is achieved. The individual oxides are present in the following proportions:

Das Glas enthält 4 bis < 6,5 Gew.-% MgO und > 4,5 bis 8 Gew.-% CaO. Eher hohe Anteile an den beiden Komponenten wirken sich positiv auf die gewünschten Eigenschaften niedrige Dichte und niedrige Verarbeitungstemperatur aus, während eher geringe Anteile die Kristallisationsbeständigkeit und die chemische Beständigkeit begünstigen.The glass contains 4 to <6.5 wt.% MgO and> 4.5 to 8 wt.% CaO. Rather high proportions of the two components have a positive effect on the desired Low density and low processing temperature properties while rather low levels of crystallization resistance and promote chemical resistance.

Weiter enthält das Glas BaO, und zwar wenigstens 0,5 Gew.-%. Der BaO-Höchstgehalt ist auf weniger als 5 Gew.-% beschränkt. So werden die gute Schmelzbarkeit gewährleistet und die Dichte niedrig gehalten.Further, the glass contains BaO, at least 0.5 wt .-%. The BaO maximum level is limited to less than 5 wt .-%. That's how the good ones become Ensuring meltability and keeping the density low.

Das Glas kann weiterhin bis zu < 4 Gew.-% des ebenfalls vergleichsweise schweren Erdalkalioxides SrO enthalten. Die Beschränkung dieser fakultiven Komponente auf diesen geringen Höchstgehalt ist insbesondere für eine geringe Dichte und eine gute Schmelzbarkeit des Glases vorteilhaft. Zur Verbesserung der Kristallisationsstabilität ist es bevorzugt, daß SrO vorhanden ist, und zwar vorzugsweise mit wenigstens 0,2 Gew.-%.The glass can also be up to <4 wt .-% of also comparatively heavy alkaline earth oxide containing SrO. The limitation of this facultative Component to this low maximum level is especially for a low Density and good meltability of the glass advantageous. For improvement For crystallization stability, it is preferred that SrO be present is, preferably at least 0.2 wt .-%.

Der Gesamtgehalt an BaO und SrO beträgt dabei wenigstens > 3 Gew.-%, um eine ausreichende Kristallisationsstabilität zu gewährleisten. The total content of BaO and SrO is at least> 3 wt .-%, to to ensure adequate crystallization stability.

Das Glas kann bis zu 2 Gew.-% ZnO, bevorzugt bis zu < 2 Gew.-% ZnO, enthalten, ZnO hat als Netzwerkwandler eine gerüstlockernde Funktion, und es hat einen geringen Einfluß auf die thermische Ausdehnung als die Erdalkalioxide. Es hat einen ähnlichen Einfluß auf die Viskositätskennlinie wie B2O3. Vorzugsweise, insbesondere bei einer Verarbeitung des Glases im Floatverfahren, ist der ZnO-Anteil auf höchstens 1,5 Gew.-% beschränkt. Höhere Anteile würden die Gefahr störender ZnO-Beläge auf einer Glasoberfläche erhöhen, die sich durch Verdampfung und anschließende Kondensation. im Heißformgebungsbereich bilden können.The glass can contain up to 2% by weight of ZnO, preferably up to <2% by weight of ZnO. ZnO has a framework-loosening function as a network converter and has little influence on the thermal expansion of the alkaline earth oxides. It has a similar influence on the viscosity characteristic as B 2 O 3 . Preferably, in particular in a processing of the glass in the float process, the ZnO content is limited to at most 1.5 wt .-%. Higher levels would increase the risk of interfering ZnO deposits on a glass surface resulting from evaporation and subsequent condensation. can form in the hot forming area.

Das Glas ist alkalifrei. Unter alkalifrei wird hierbei verstanden, daß es im wesentlichen frei ist von Alkalioxiden, wobei es Verunreinigungen von weniger als 1000 ppm enthalten kann.The glass is alkali-free. Alkaline-free is here understood to mean essentially is free of alkali oxides, with impurities of less may contain as 1000 ppm.

Die Gläser können bis zu 2 Gew.-% ZrO + TiO2 enthalten, wobei sowohl der TiO2-Gehalt als auch der ZrO2-Gehalt einzeln bis zu 2 Gew.-% betragen kann. ZrO2 erhöht vorteilhaft die Temperaturstabilität des Glases. Aufgrund seiner Schwerlöslichkeit erhöht es jedoch die Gefahr von ZrO2-haltigen Schmelzrelikten (sog. "Zirkonnester") im Glas. Daher wird vorzugsweise auf die Zugabe von ZrO2 verzichtet. Geringe Gehalte an ZrO2, die von der Korrosion zirkonhaltigen Wannenmaterials herrühren, sind unproblematisch. TiO2 setzt vorteilhaft die Solarisationsneigung, d. h. die Abnahme der Transmission im sichtbaren Wellenlängenbereich aufgrund von UV-VIS-Strahlung, herab. Bei Gehalten von mehr als 2 Gew.-% können durch Komplexbildung mit Fe3+-lonen, die im Glas in geringen Gehalten infolge von Verunreinigungen der eingesetzten Rohstoffe vorhanden sind, Farbstiche auftreten.The glasses can contain up to 2% by weight ZrO + TiO 2 , wherein both the TiO 2 content and the ZrO 2 content individually can be up to 2% by weight. ZrO 2 advantageously increases the temperature stability of the glass. However, due to its poor solubility, it increases the risk of ZrO 2 -containing melt relics (so-called "zircon nests") in the glass. Therefore, it is preferable to dispense with the addition of ZrO 2 . Low levels of ZrO 2 , which result from the corrosion zirkonhaltigen tub material, are not a problem. TiO 2 advantageously lowers the solarization tendency, ie the decrease in the transmission in the visible wavelength range due to UV-VIS radiation. At levels greater than 2% by weight, color casts may occur by complexing with Fe 3+ ions present in the glass at low levels due to impurities in the raw materials used.

Die Gläser können herkömmliche Läutermittel in herkömmlichen Mengen enthalten: So kann es bis zu 1,5 Gew.-% As2O3, Sb2O3, SnO2 und/oder CeO2 enthalten. Auch ist der Zusatz von je 1,5 Gew.-% Cl- (beispielsweise als BaCl2), F-(z. B. als CaF2) oder SO4 2- (z. B. als BaSO4) möglich. Die Summe aus As2O3, Sb2O3, CeO2, SnO2, Cl-, F- und SO4 2- soll jedoch 1,5 Gew.-% nicht überschreiten.The glasses may contain conventional refining agents in conventional amounts: for example, it may contain up to 1.5% by weight of As 2 O 3 , Sb 2 O 3 , SnO 2 and / or CeO 2 . It is also possible to add 1.5% by weight of Cl - (for example as BaCl 2 ), F - (for example as CaF 2 ) or SO 4 2- (for example as BaSO 4 ). However, the sum of As 2 O 3 , Sb 2 O 3 , CeO 2, SnO 2, Cl - , F - and SO 4 2- should not exceed 1.5% by weight.

Wenn auf die Läutermittel As2O3 und Sb2O3 verzichtet wird, sind die Gläser nicht nur mit den verschiedenen Ziehverfahren, sondern auch mit dem Floatverfahren verarbeitbar. If the refining agents As 2 O 3 and Sb 2 O 3 are dispensed with, the glasses can be processed not only with the different drawing methods but also with the float method.

Beispielsweise im Hinblick auf eine einfache Gemengezubereitung ist es von Vorteil, daß sowohl auf ZrO2 als auch auf SnO2 verzichtet werden kann und dennoch Gläser mit dem genannten Eigenschaftsprofil, insbesondere mit hoher thermischer und chemischer Beständigkeit und mit geringer Kristallisationsneigung, erhalten werden.For example, with regard to a simple batch preparation, it is advantageous that both ZrO 2 and SnO 2 can be dispensed with and still glasses with the mentioned property profile, in particular with high thermal and chemical resistance and with low crystallization tendency, are obtained.

Ausführungsbeispiele:EXAMPLES

Aus herkömmlichen, von unvermeidlichen Verunreinigungen abgesehen im wesentlichen alkalifreien, Rohstoffen wurden bei 1620°C Gläser in Pt/lr-Tiegeln erschmolzen. Die Schmelze wurde anderthalb Stunden bei dieser Temperatur geläutert, anschließend in induktiv beheizte Platintiegel umgegossen und zur Homogenisierung 30 Minuten bei 1550°C gerührt.From conventional, apart from inevitable impurities in the Raw materials were at 1620 ° C glasses in Pt / lr crucibles melted. The melt was at this for one and a half hours Purified temperature, then poured into inductively heated platinum crucible and stirred for 30 minutes at 1550 ° C for homogenization.

Die Tabelle zeigt 11 Beispiele erfindungsgemäßer Gläser mit ihren Zusammensetzungen (in Gew.-% auf Oxidbasis) und ihren wichtigsten Eigenschaften. Das Läutermittel SnO2 mit einem Anteil von 0,3 Gew.-% ist nicht aufgeführt. Folgende Eigenschaften sind angegeben:

  • der thermische Ausdehnungskoeffizient α20/300 [10-6/K]
  • die Dichte p [g/cm3]
  • die dilatometrische Transformationstemperatur Tg [°C] nach DIN 52324
  • die Temperatur bei der Viskosität 104 dPas (bezeichnet als T 4 [°C])
  • die Temperatur bei der Viskosität 102 dPas (bezeichnet als T2 [ °C], berechnet aus der Vogel-Fulcher-Tammann-Gleichung
  • der Brechwert nd
  • eine Säurebeständigkeit "HCl" als Gewichtsverlust (Abtragswert) von allseitig polierten Glasplättchen der Abmessungen 50 mm x 50 mm x 2 mm nach Behandlung mit 5 %iger Salzsäure für 24 Stunden bei 95°C [mg/cm2].
  • die Beständigkeit gegenüber gepufferter Fluorwasserstoffsäure "BHF" als Gewichtsverlust (Abtragswert) vonallseitig polierten Glasplättchen der Abmessungen 50 mm x 50 mm x 2 mm nach Behandlung mit 10 % iger NH4F · HF für 20 Min. bei 23 °C [mg/cm2].
Beispiele: Zusammensetzungen (in Gew.-% auf Oxidbasis) und wesentliche Eigenschaften von erfindungsgemäßen Gläsern. 1 2 3 4 5 6 SiO2 59,0 58,5 58,5 60,0 58,5 60,7 B2O3 7,0 6,5 6,5 6,6 8,1 6,5 Al2O3 20,5 21,2 21,2 21,2 21,2 20,2 MgO 4,5 4,5 4,5 4,2 4,2 4,2 CaO 5,0 5,0 5,0 4,6 4,6 4,8 SrO 1,9 0,5 3,5 2,6 2,6 2,8 BaO 1,8 3,5 0,5 0,5 0,5 0,5 ZnO - - - - - - α 20/300 [10-6/K] 3,44 3,42 3,55 3,31 3,33 3,37 p [g/cm3] 2,50 2,52 2,52 2,48 2,48 2,48 Tg[°C] 741 747 742 749 738 745 T 4 [°C) 1279 1285 1263 1293 1276 1292 T 2 [°C] 1629 1632 1620 1648 1627 1650 nd 1,526 1,528 1,528 1,524 1,524 1,523 HCl [mg/cm2] 0,88 0,76 n. b. n. b. n. b. 0,68 BHF [mg/cm21 0,66 0,65 0,73 0,67 0,67 0,65 n. b.= nicht bestimmt
(Fortsefzung der Tabelle s. nächste Seite) 7 8 9 10 11 SiO2 59,5 59,3 58,3 58,5 58,2 B2O3 7,5 6,1 6,1 6,5 7,2 Al2O3 20,2 20,2 20,2 22,8 20,9 MgO 4,2 6,0 6,0 4,1 4,1 CaO 4,8 4,8 4,8 4,6 6,0 SrO 2,8 2,8 2,8 0,2 0,2 BaO 0,5 0,5 0,5 3,0 3,1 ZnO - - 1,0 - - α 20/300 [10-6/K] 3,38 3,54 3,57 3,24 3,47 p [g/cm3 2,48 2,51 2,53 2,50 2,51 Tg[°C] 736 744 738 756 740 T4[°C] 1278 1271 1255 1298 1264 T2[°C] 1633 1617 1695 1647 1624 Nd 1,523 1,529 1,531 1,526 1,528 HCl [mg/cm2] n. b. 0,67 0,66 0,94 n. b. BHF [mg/cm2] 0,66 0,74 0,77 0,64 0,62 n. b.= nicht bestimmt The table shows 11 examples of glasses according to the invention with their compositions (in% by weight based on oxide) and their most important properties. The refining agent SnO 2 with a proportion of 0.3 wt .-% is not listed. The following properties are specified:
  • the thermal expansion coefficient α 20/300 [10 -6 / K]
  • the density p [g / cm 3 ]
  • the dilatometric transformation temperature T g [° C] according to DIN 52324
  • the temperature at the viscosity 10 4 dPas (referred to as T 4 [° C])
  • the temperature at the viscosity 10 2 dPas (referred to as T2 [° C] calculated from the Vogel-Fulcher-Tammann equation
  • the refractive index n d
  • an acid resistance "HCl" as weight loss (removal value) of all-round glass plates of dimensions 50 mm × 50 mm × 2 mm after treatment with 5% hydrochloric acid for 24 hours at 95 ° C. [mg / cm 2 ].
  • the resistance to buffered hydrofluoric acid "BHF" as weight loss (Abtragswert) of all sides polished glass plates of dimensions 50 mm x 50 mm x 2 mm after treatment with 10% NH 4 F · HF for 20 min. At 23 ° C [mg / cm 2 ].
Examples: Compositions (in% by weight based on oxides) and essential properties of glasses according to the invention. 1 2 3 4 5 6 SiO 2 59.0 58.5 58.5 60.0 58.5 60.7 B 2 O 3 7.0 6.5 6.5 6.6 8.1 6.5 Al 2 O 3 20.5 21.2 21.2 21.2 21.2 20.2 MgO 4.5 4.5 4.5 4.2 4.2 4.2 CaO 5.0 5.0 5.0 4.6 4.6 4.8 SrO 1.9 0.5 3.5 2.6 2.6 2.8 BaO 1.8 3.5 0.5 0.5 0.5 0.5 ZnO - - - - - - α 20/300 [10 -6 / K] 3.44 3.42 3.55 3.31 3.33 3.37 p [g / cm 3 ] 2.50 2.52 2.52 2.48 2.48 2.48 T g [° C] 741 747 742 749 738 745 T 4 [° C] 1279 1285 1263 1293 1276 1292 T 2 [° C] 1629 1632 1620 1648 1627 1650 n d 1,526 1,528 1,528 1.524 1.524 1.523 HCl [mg / cm 2 ] 0.88 0.76 nb nb nb 0.68 BHF [mg / cm 2 1 0.66 0.65 0.73 0.67 0.67 0.65 nb = not determined
(Continuation of the table see next page) 7 8th 9 10 11 SiO 2 59.5 59.3 58.3 58.5 58.2 B 2 O 3 7.5 6.1 6.1 6.5 7.2 Al 2 O 3 20.2 20.2 20.2 22.8 20.9 MgO 4.2 6.0 6.0 4.1 4.1 CaO 4.8 4.8 4.8 4.6 6.0 SrO 2.8 2.8 2.8 0.2 0.2 BaO 0.5 0.5 0.5 3.0 3.1 ZnO - - 1.0 - - α 20/300 [10 -6 / K] 3.38 3.54 3.57 3.24 3.47 p [g / cm 3 2.48 2.51 2.53 2.50 2.51 T g [° C] 736 744 738 756 740 T4 [° C] 1278 1271 1255 1298 1264 T2 [° C] 1633 1617 1695 1647 1624 N d 1.523 1,529 1,531 1,526 1,528 HCl [mg / cm 2 ] nb 0.67 0.66 0.94 nb BHF [mg / cm 2 ] 0.66 0.74 0.77 0.64 0.62 nb = not determined

Wie die Ausführungsbeispiele verdeutlichen, besitzen die erfindungsgemäßen Gläser folgende vorteilhafte Eigenschaften:

  • eine thermische Dehnung α 20/300 zwischen 2,8 10-6/K und 3,6 x 10-6/K, damit angepaßt an das Ausdehnungsverhalten von amorphen und auch zunehmend polykristallinem Silicium.
  • mit Tg > 700 °C eine hohe Transformationstemperatur, also eine hohe Temperturbeständigkeit. Dies ist wesentlich für einen möglichst geringen herstellungsbedingten Schrumpf ("compaction") und für die Verwendung der Gläser als Substrate für Beschichtungen mit amorphen Si-Schichten und deren anschließende Temperung.
  • mit ρ < 2,600 g/cm3 eine geringe Dichte
  • eine Temperatur bei der Viskosität 104 dPas von maximal 1350 °C, und eine Temperatur bei der Viskosität 102 dPas von maximal 1720 °C, was hinsichtlich der Heißformgebung sowie Schmelzbarkeit eine geeignete Viskositätskennlinie bedeutet. Die Gläser sind als Flachgläser mit den verschiedenen Zieverfahren, z. B. Micro-sheet-Down-draw-, Up-draw-oder Overflow-fusion-Verfahren und in bevorzugter Ausführung, wenn sie frei von As2O3 und Sb2O3 sind, auch mit dem Floatverfahren herstellbar.
  • eine hohe chemische Beständigkeit, dokumentiert durch gute Beständigkeit gegenüber Salzsäure und gegenüber gepufferter Flußsäurelösung, was sie ausreichend inert gegen die bei der Herstellung von Flachbildschirmen verwendeten Chemikalien macht.
  • mit nd ≤1,531 einen geringen Brechwert. Diese Eigenschaft ist physikalische Grundlage für eine hohe Transmission.
As the exemplary embodiments make clear, the glasses according to the invention have the following advantageous properties:
  • a thermal expansion α 20/300 between 2.8 10 -6 / K and 3.6 x 10 -6 / K, thus adapted to the expansion behavior of amorphous and increasingly polycrystalline silicon.
  • with T g > 700 ° C a high transformation temperature, ie a high Temperturbeständigkeit. This is essential for the lowest possible production-related shrinkage ("compaction") and for the use of the glasses as substrates for coatings with amorphous Si layers and their subsequent heat treatment.
  • with ρ <2.600 g / cm 3 a low density
  • a temperature at the viscosity 10 4 dPas of at most 1350 ° C, and a temperature at the viscosity 10 2 dPas of at most 1720 ° C, which means a suitable viscosity characteristic in terms of hot molding and meltability. The glasses are flat glasses with the different Zieverfahren, z. As micro-sheet down-draw, up-draw or overflow-fusion process and in a preferred embodiment, if they are free of As 2 O 3 and Sb 2 O 3 , can also be produced by the float process.
  • high chemical resistance, documented by good resistance to hydrochloric acid and to buffered hydrofluoric acid solution, rendering it sufficiently inert to the chemicals used in the manufacture of flat panel displays.
  • with n d ≤ 1.531 a low refractive index. This property is the physical basis for high transmission.

Die Gläser weisen einen hohe Temperaturwechselbeständigkeit und eine gute Entglasungsstabilität auf.The glasses have a high thermal shock resistance and good Devitrification stability on.

Damit sind die Gläser hervorragend geeignet für die Verwendung als Substratglas in der Displaytechnik, insbesondere für TFT-Displays, und in der Dünnschicht-Photovoltaik.This makes the glasses ideal for use as a substrate glass in display technology, especially for TFT displays, and in the Thin film photovoltaics.

Claims (7)

  1. Alkali-free aluminoborosilicate glass which has the following composition (in % by weight, based on oxide): SiO2 > 58 - 65 B2O3 > 6 - 11.5 Al2O3 > 20 - 25 MgO 4 - < 6.5 CaO > 4.5 - 8 SrO 0 - < 4 BaO 0.5 - < 5 with SrO + BaO > 3 ZnO 0 - 2
  2. Aluminoborosilicate glass according to Claim 1, characterized in that it comprises at least 20.5% by weight, preferably more than 21% by weight, of Al2O3.
  3. Aluminoborosilicate glass according to Claim 1 or 2, characterized by the following composition (in % by weight, based on oxide): ZrO2 0 - 2 TiO2 0 - 2 with ZrO2 + TiO2 0 - 2 As2O3 0 - 1.5 Sb2O3 O - 1.5 SnO2 O - 1.5 CeO2 O - 1.5 C1- 0 - 1.5 F- 0 - 1.5 SO4 2- 0 - 1.5 with AS2O3 + Sb2O3 + SnO2 + CeO2 0 - 1.5 + C1 + F- + SO4 2-
  4. Aluminoborosilicate glass according to at least one of Claims 1 to 3, characterized in that the glass is free of arsenic oxide and antimony oxide, apart from unavoidable impurities, and that it can be produced in a float-glass plant.
  5. Aluminoborosilicate glass according to at least one of Claims 1 to 4, which has a coefficient of thermal expansion α20/300 of 2.8 · 10-6/K-3.6 . 10-6 /K, a glass transition temperature Tg of > 700°C and a density p of < 2.600 g/cm3.
  6. Use of the aluminoborosilicate glass according to at least one of Claims 1 to 5 as substrate glass in display technology.
  7. Use of the aluminoborosilicate glass according to at least one of Claims 1 to 6 as substrate glass in thin-film photovoltaics.
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